Vinylidene chloride-trichlorobromo-methane reaction products



United States Patent VINYLIDENE CHLORIDE-TRICHLOROBROMO- METHANEREACTION PRODUCTS No Drawing. Application November 30, 1956 Serial No.625,229

3 Claims. (Cl. 260-658) This invention relates to liquid vinylidenechloride-trichlorobromomethane reaction products useful as insecticidesand as intermediates in the preparation of other halogenated aliphatichydrocarbon derivatives, particularly by substitution of fluorine forchlorine, as disclosed in our copending application Serial No. 314,566,filed August 8, 1952, entitled Organic Compound and Method of ProducingSame.

The invention also relates to methods of preparing the above disclosedvinylidene chloride-trichlorobromornethane reaction products with highyields.

In proceeding according to the present invention, vinylidene chloride isreacted with trichlorobromomethane in the presence of an additionpolymerization initiator. The details of this reaction are disclosed asfollows.

' The polymerization initiators which are suitable for the presentinvention are any of the polymerization initiators known in the art forpolymerizing addition polymerizable mono olefins such as vinylidenechloride and vinylidene fluoride. Particularly useful are the peroxidessuch as benzoyl peroxide, tertiary butyl peroxide, lauryl peroxide andacetyl peroxide. In general, any

agent that decomposes thermally to give free radicals, or'

causes the generation of free radicals, is useful in initiatingpolymerization of the mono olefin addition monomers. For example, ultraviolet light, lead tetraethyl and azides may also be used. Suitablechemical initiators are characterized by the fact that they produce freeradicals by thermal decomposition and must decompose at the temperatureof the reaction.

The quantity of initiator utilized will depend upon the particularcharacteristics of the specific initiator being used, thesecharacteristics being well known inthe art and forming no part ofthepresent invention. In the case of benzoyl peroxide, a concentrationof 1.0 mole percent of this peroxide based on the amount of vinylidenechloride is used. As little as 0.01 mole percent and up to 5 molepercent or more can be used eflectively. Other peroxides are used insimilar amounts.

The reaction may be carried out at a temperature of 0? C. or lower. If achemical initiator is used, the tem perature is one at which theinitiator decomposes to free radicals. The decomposition temperature ofany given polymerization initiator is well known and forms no part ofthepresent invention. In the case of benzoyl peroxide the temperature maybe as low as 60 C. and as high as 100 C. Similar temperatures are usedfor other peroxides. If it is desired to operate at lower temperaturesusing peroxide or other peroxide initiators, various compounds such asaromatic amines (aniline, toluidine and the like) may be added to thereaction mixture, and then temperatures as low as 0 C. may be used.

Preferably, the reaction is carried out in sealed vessels utilizing theautogenous pressure of the reactants, although superatmosphericpressures generated by other means can also be employed and pressuresabove or below the autogenous pressure may be used. In general,

say, for some insecticidal purposes.

the pressure to be employed will depend on any solvent or diluent beingused but largely upon the specific initiator employed, since generallythe temperature will determine the pressure for any given reactionmixture. In the case of benzoyl peroxide, a suitable pressure would beabout 50 pounds per square inch, and similar pressures would be usedwith other peroxides.

The reaction time may range from 24 hours or less to hours or more. Inthe case of benzoyl peroxide and other peroxide initiators, a reactiontime of almost 50 hours is convenient.

A large excess of trichlorobromomethane is used, since the proportionsof liquid reaction products obtained to solid reaction products dependsupon the ratio of trichlorobromomethane to vinylidene chloride. The moleratio should be at least about 10:1 and may be 20:1 or higher. Thetrichlorobromomethane also functions as a solvent and/or diluent. Othersolvents and/or dil'uents may also be used, if desired, such as theabove noted aromatic amines, as long as the reaction mass contains thetwo reactants in the above disclosed mole ratio.

The reaction of the present invention yields, besides the desired liquidend product, small amounts of two solid by-products of higher molecularWeight. One of these by-products is insoluble in trichlorobromomethane,and therefore also in the final reaction mass. This byproduct(hereinafter referred to as product I) has a molecular Weight range offrom 1000 to 5000 and a melting point of C. It may be separated from thefinal reaction mass by simple filtration, which leaves a filtratecontaining trichlorobromomethane having dissolved therein the secondsolid by-product and the desired liquid end product. i

The second solid and product (hereinafter referred to as product II) hasa molecular weight range of from 100 to 1100 and a melting point of from30 to 40 C. It is soluble in trichlorobromornethane but insoluble inpetroleum ether, and in trichlorotrifluoroethane and other liquidhydrocarbon and/or halogenated hydrocarbons of like polarity and boilingpoint or boiling range. Product II may be separated from the finalreaction mass (after product I has been separated therefrom) bydistilling off, from the final reaction mass, the excess and thereforeunreacted trichlorobrornomethane, which leaves a waxy substancecontaining product 11 and the desired liquid end product (hereinafterreferred to as product III); digesting the waxy residue with petroleumether or trichlorotrifluoroethane or some other liquid hydrocarbon orhalogenated hydrocarbon of like polarity and boiling point or boilingrange, which will dissolve product III but not product II; and filteringoff the undissolved product II. This leaves a solution of product III inthe petroleum ether or trichlorotrifluoromethane or like solvent.Product III may be recovered, free from products I and II, by distillingoif this solvent.

It should be understood that for many purposes it may not be necessaryto isolate product 111 (the desired liquid end product) from product Ior from product 11 or from both products I and II. The latter twoproducts do not necessarily interfere with the use of product iii,Hence, if desired, the final reaction mass may be subjected todistiliation, with or Without prior removal of product I by filtration,to remove the excess, unreacted trichlorobromomethane, which would leavea more or less waxy residue containing products II and III and alsoproduct I if the latter Examples I and II show reactions according tothe present Patented Apr. 22, 1958.

Example I A commercial sample of vinylidene chloride containing apolymerization inhibitor was washed with a 5% aqueous solution of sodiumhydroxide to remove the inhibitor. The product from the extraction stepwas washed with water to remove any excess residual sodium hydroxide andthereafter dried over Drierite to remove the water. The resultantproduct was an actively polymerizable vinylidene chloride.

97.0 grams or 1 mole of the active polymelizable vinylidene chloride wasmixed with 1980 grams or moles of trichlorobromomethane and 2.42 gramsor 0.01 mole of benzoyl peroxide. The mixture was then transferred toPyrex pressure bottles and neoprene stoppers were wired on. The loadedbottles were placed in an oil bath maintained at a temperature of 70.5C.i0.5 C. After 50 hours the bottles were removed from the bath and theproduct was cooled to room temperature. The cooled product was thenfiltered through a Buechner funnel to separate that portion of theproduct which was insoluble in the trichlorobromomethane solution. Thisportion of the product is hereinafter designated fraction I. Thetrichlorobromomethane was next removed from the filtrate by distillationat reduced pressures using an oil bath for heating. The last portion ofsolvent was removed at a pressure of 20 mm. Hg, absolute, at a maximumbath temperature of 70 C.

The product from the distillation step was a waxy residue. This residuewas further separated into a liquid and a solid fraction by agitationwith low boiling petroleum ether followed by filtration. The solidfraction removed by filtration will hereinafter be referred to asfraction II. The solvent was removed from the filtrate by distillationand a liquid polymer fraction was recovered. This liquid fraction ishereinafter referred to as fraction III.

This reaction yielded 34.0 grams of fraction I, 11.0 grams of fractionII, and 90.0 grams of fraction III. The molecular weights of the variousfractions were determined by the boiling point or ebullioscopic methodemploying benzene as the solvent. The following values were obtained'for the molecular weights: fraction I, 5,0001,000; fraction II,1,100-100; and fraction III, 500-50.

Fraction III was a liquid at room temperature, whereas fraction II was asolid melting at 30 to 40 C. and fraction I was a solid melting at about140 C.

Fraction III constituted 65% of the total product.

Example II The procedure in Example I was carried out again, thereactants, polymerization temperature and monomer and peroxidequantities being the same, except that the mole ratio oftrichlorobromomethane to monomer used was 20/1 instead of 10/1. Thisreaction yielded 10 grams of fraction I, 10 grams of fraction II, and117 grams of fraction III. Fraction III, the desired liquid product,constituted 85% of the total product. The amount of higher molecularweight products was correspondingly decreased.

Example III The procedure followed in Example I was again repeated, allreactants, polymerization temperature, and monomer and peroxidequantities being the same, except that the mole ratio oftrichlorobromomethane to monomer used, was 5/1 instead of 10/ 1. In thisreaction the following amounts of products were obtained: 54 grams 4 offraction I, 30 grams of fraction II and fraction III combined. Thus lessthan 36% of the total product was contained in the liquid fraction III.

It should be understood that fraction III referred to in the aboveexamples is the desired liquid end product (herein also referred to asproduct III). This fraction III, or product III, is, as disclosed above,a liquid being a molecular weight range of from 50 to 500.

It is believed that products I, II and III all have the generalstructural formula It is further believed that product III is primarilya mixture of two compounds wherein the value of N is 3 and 4. Inproducts II and III, the value of N exceeds 4.

As disclosed hereinabove, methods are set forth in our co-pendingapplication Serial No. 314,566, filed October 13, 1952, entitled,Organic Compound and Method of Producing Same, for producing, fromproduct III, a thermally stable, liquid, fluorine containingcomposition.

Further, product III possesses insecticidal properties, as illustratedby the following experiment.

Various percentages (by weight) of product III were incorporated inflour. Confused flour beetle (Tribolium confusum, Duv.) adults wereexposed to the treated flour. Specifically, the test material (productIII) was dissolved in carbon tetrachloride and the resulting solutionwas mixed with flour in such quantity that the flour contained 10% (byweight) of product III. After the carbon tetrachloride had evaporated,portions of the 10% mixture were diluted with flour to give mixturescontaining 5%, 1%, 0.1% and 0.01% of product III. For controls flour wasused to which carbon tetrachloride had been added and then evaporated.Duplicate portions of 10 gram portions of flour of each concentration ofproduct III were placed in 2 ounce jars, and twenty adult fiour beetleswere added to each jar. There wasno immediate knockdown (i. e. in thefirst two hours) at any concentration. The data with respect toknockdown and percent mortality are given in the following table:

24 hours 48 hours one week Product III, percent by weightknockknockdead,

down, down, percent percent percent 1 Removed to untreated flour at thistime.

None of the beetles in this test recovered after having been knockeddown even when they were removed to untreated flour. The beetles exposedto flour containing 0.01% of product III appeared less active than thosein the controls.

This application is a continuation-in-part of our allowed applicationSerial No. 303,430, filed August 8, 1952, now abandoned, entitledVinylidene Chloridetrichlorobromomethane Reaction Products.

Many details may be varied without departing from the principles of thisinvention and it is therefore not our intention to limit the patentgranted on this invention otherwise than necessitated by the scope ofthe appended claims.

The invention is claimed as follows:

1. A method of producing a liquid organic product soluble in low boilingpetroleum ether and having a molecular weight ranging from 50 to 500,said method comprising reacting one mole of vinylidene chloride with atleast 10 moles of trichlorobromomethane, said reaction being carried outin the presence of a polymerization initiator, cooling the resultantreaction mass, filtering the cooled reaction mass to separate a materialinsoluble in said cooled reaction mass, distilling off unreactedtrichlorobromornethane from the filtrate, and extracting from theresidual material the said liquid product with a solvent selected fromthe group consisting of petroleum ether and trichlorotrifluoro ethane.

2. A method of producing a liquid organic product soluble in low boilingpetroleum ether and having a molecular Weight ranging from 50 to 500,said method comprising reacting one mole of vinylidene chloride with atleast moles of trichlorobromomethane, said reaction being carried out inthe presence of benzoyl peroxide and at a temperature at which benzoylperoxide decomposes to give free radicals and at the autogenous pressureof the reaction mass, thereafter cooling the resultant reaction mass,filtering the cooled reaction mass to separate a material insoluble insaid cooled reaction mass, distilling ofi unreactedtrichlorobromomethane from the filtrate, and extracting from theresidual material the said liquid product with a solvent selected fromthe group consisting of petroleum ether and trichlorotrifluoro ethane.

3. A liquid organic product soluble :in carbon tetrachloride. in lowboiling petroleum ether and in trichlorotrifluoro ethane, said producthaving a molecular weight ranging from to 500 and being the product of areaction of one mole of vinylidene chloride with at least 10 moles oftrichlorobromometliane in the presence of a polymerization initiator.

References Cited in the file of this patent UNITED STATES PATENTS2,440,800 Hanford et al. May 4, 1948 2,468,208 Kharasch Apr. 26, 1949FOREIGN PATENTS 620,855 Great Britain Mar. 31, 1949 649,555 GreatBritain Jan. 31, 1951 OTHER REFERENCES Kharasch et al.: .1 our. Am.Chem. Soc., vol. 69, pages 1100-1110 (1947).

1. A METHOD OF PRODUCING A LIQUID ORGANIC PRODUCT SOLUBLE IN LOW BOILINGPETROLEUM ETHER AND HAVING A MOLECULAR WEIGHT RANGING FROM 50 TO 500,SAID METHOD COMPRISING REACTING ONE MOLE OF VINYLIDENE CHOLORIDE WITH ATLEAST 10 MOLES OF TRICHLOROBROMOMETHANE, SAID REACTION BEING CARRIED OUTIN THE PRESENCE OF A POLYMERIZATION INITIATOR, COOLING THE RESULTANTREACTION MASS, FILTERING THE COOLED REACTION MASS TO SEPARATE A MATERIALINSOLUBLE IN SAID COOLED REACTION MASS, DISTILLING OFF UNREACTEDTRICHLOROBROMOMETHANE FROM THE FILTERATE, AND EXTRACTING FROM THERESIDUAL MATERIAL THE SAID LIQUID PRODUCT WITH A SOLVENT SELECTED FROMTHE GROUP CONSISTING OF PETROLEUM ETHER AND TRICHLOROTRIFLUORO ETHANE.